New diazo-amino compounds



Patented Aug. 16, 1932 TUNITEDSTATES PAT-Eur r ce WINFRID HENTRICH, or LEvERKUsnN-wIEsDoRr, nansr rrrrrzn, or screens-Burns,

ANTON OSSENBECK, F COLOGNE-MULHEIM, AND rErnaBaoKas-or GLADBACH- RHEYDT, GERMANY, assrenons T0 GENERAL ANILINE WORKS, me, or NEW YORK,

N. Y., A CORPORATION OF DELAWARE 7 NEW DIAZO-AMINO ooMrouNns "No Drawing: Application flied September 17,1931,

I The present invention relates to new diazo-amino compounds, more particularly it relates to compounds of the probable general formula: V 7

R--N=N-NH- B wherein R standsfor' theradical of a diazotizable amine suitable for producing azodyestuffs which is at least once substituted by a substituent selected from the group consisting of the sulfonic acid group, the carboxylic acid group, a carboxylic acid ester group, the aryl-sulfone group, the nitro group andhalogem-and which may be further substituted by alkyl or alkoxy, n stands for one of the numbers one to three, and wherein the benzene nucleus :13 may be further substituted by substituents of'the group consisting of alkyl, alkoxy, halogen.

obtainable -Onr new compounds are causing to react upon each other, advantageously in about molecular quantities and at a low temperature, say at temperatures not higher thanabout 30%0 0., adiazonium compound obtained in the usual manner nitrite and hydrochloric acid and introduce the same into an aqueous solution of van amino benzene mono-, dior tri-sulfonic acid. The formation of the new diazoamino compounds proceeds extremely smoothly either in alkaline, neutraland weakly acid "aqueous solution. From the concentrated so- Serial No. 563,458, and in Germany July 14, 1928.

lutions the new diazoamino compounds often partially separate during the reaction, especially when working in acid solution. The

separation can be completed by the addition of a suitable salt, such as common salt. .-After' carefully drying, the new products are generally obtained in form of greyish to orange crystalline powders. The action of acid reagents, such .as formic acid, acetic acid, oxalic acid and sodium ,bisulfate, on the aqueous solutionsof the saltof the new diazoamino compounds causes in a very short time a smooth and quantitive reconversion into the diazo compound and the aminobenzene'sulfonic acid used in the formation .of s the diazoamino compound Furthermore, the new products are stable towards heat, percussion, friction and neutral and al- 'kallne substances, such as Glaubers salt, so-

dium carbonate, potassium carbonate and the like.

The new compounds are intended to find application in dyeing and printing and also for combating insect pests. v.

; p The following examples will illustrate our invention, without limiting it thereto: 7

Ezcwmple 1.2 l,3 parts by weight of 2.5-

dichloro-1-aminobenzenei-sulfonic acid are diazotized in the usual manner, and the diazo solution issiowly run into the solution of 36 parts by Weight of aniline-2.5-disulfonic acid. lhe reaction mixture is neutralized by the addition of sodium acetate until neutral to Congo, and the new diazo-amino compound having in the free state the following formula:1

c1 sonar:

is salted out, sucked off, centrifuged and dried by gently heating.

' HOaS- sulfonic acid there can be used .2-amino-4'- methyl 1..1-diphenylsulfone-4c-sulfonicl acid or 2-amino-4-hydroXy-l.l-diphenylsulfonei 3 -carbox ylic acidiesulfonic acid or the 2- amino-1,1 -diphenyl'sulfone itself.

Instead of 2.5-dichloro-l-aminobenzene-- J dried at a moderate temperature.

acid in aqueous solution.

E wample 2.152 parts by weight of 5-nitro-2-amino-1-methylbenzene are diazotized in the usual manner in hydrochloric acid solution in sodium nitrite. The filterd diazo solution is quickly introduced at about 20 C. in the neutral solution of the sodium salt of 360 parts by weight of technical aniline-2.5- disulfonic acid in 1000 parts of water. The acid reaction of the solution is then neutralized with sodium acetate until neutral to Congo, and the reaction product is salted out by the addition of common salt. amino compound, having in its free state the following formula:

is sucked off after some time, centrifuged and lowish orange crystalline powder, easily soluble in water, stable towards heat, percussion and friction. By the action of weak and strong acids or acid reacting salts it is split up into its components quickly and quantitatively.

In quite an analogous manner there is ob tainable a diazo-amino compound of similar properties when the diazonium chloride solution above described is caused to react upon the sodium salt of,aniline-2.4-disulfonic Example 3. 152 parts by weight of 3- nitro-1-niethyl-4-aminobenzene are diazotized in the usual manner. This solution is slowly introduced at about 20 G. into a neutral solution of rather more than the calculated quantity of aniline-2.5-disulfonic acid. The solution is neutralized by the addition of sodium acetate, and the new compound is separated by the addition of common salt. The compound, having in its free state the following formula:

soarr crystallizing in glittering yellow leaflets, is

sucked oii', centrifuged and dried at about 60 compounds having similar properties.

Example .4.In'to the aqueous solution of the diazonium chloride prepared from 183 parts by weight of QA-dinitroanilinasaid aqueous solution containing sodium acetate,

The diazo- 7 It is a yel-.

has the following formula:

aniline-2.5-disulfonic there is introduced a neutral solution of the sodium salt of rather more than the calcu lated quantity of aniline-2.5-disulfonic acid. Vhen the coupling is complete, there is obtained in a ratherquantitative yield the sodium salt of the diazoamino compound of the formula:

dichloroaniline are diazotized in the usual manner. The diazo solution is slowlyintroduced into a neutral solution of anequivalent quantity of aniline-3.5-disulfonic acid.

When the coupling is complete,--the diazoamino compound is salted out from the solu tion which previously has been neutralized by the addition of sodium acetate. It is obtained in form of a yellowish powder of good stability andsolubility. Yield nearly h quantitative.

01 I SQaH by the addition of soda solution, is salted -out by means of sodium chloride, filtered and dried. There are obtained yellow, water soluble leaflets. In its free state the compound 'Emample 7'.-233 parts by weight of 2- -aminodiphenylsulfone are dissolved in. the

equivalent quantity of acetone. This solution is added to 400 parts by weight of ice- -cold technical hydrochloricacid and quickly diazotized with an aqueous solution of' 69 parts by weight of sodium nitrite; While stirring, this 'diazo solution is introduced into a solution of'325 parts by weight of the sodium salt of I-methoxy-Q-aminobenzene-4.6-

I disulfonic-acid. When the couplingis cornplete, the diazoamino compound is saltedout from the solution which previously has been neutralized by the addition of sodium ,acetate. The Working up is effected in quite an analogous manner as described in Example 6, In its free state the compound corresponds to the following formula SO sH H3O SOaH V V Ewample 8.-185,5 parts by weight of '2- amino5-chlor0-1-benzoic acid methylester are diazotized in the usual manner. The diazo solution isneutralized by the addition of sodium acetate, to the solution there are added 329,5 parts by weight of l-aminoichlorobenzene 2.5 disodiumsulfonate, dissolved in water, The coupling enters immediately, and the diazo compound having in its free state the following formula:

sonar is salted out from the solution, rendered sodaalkaline, filtered and dried.

EwampZe-9.196 parts by weight of 2-.

amino-4-metl1yl-5-nitro-l-benzoic acid are diazotized in the usual manner with 69 parts by weight of sodium nitrite and, as described in Example '6, coupled with 209 parts by weight of the sodium salt of 1-methyl-2-aminobenzene-S-sulfonic acid. The diazoamino compound thus obtained, having in its free state the following formula.- V

coon

CH3 CH is separated as described in Example 6.

Emample 10.158 parts by weight of 5- nitro-2-amino-1methoxybenzne are diazotized in the usual manner with 69 parts by weight of sodium nitrite. The diazo solution is neutralized by the addition of sodium acetate and to' the solution there are added 329,5 partsbyweightof the sodium salt of l-amino t-chlorobenzene 2.5-disulfonic acid. The coupling enters immediately, and by salting out by means of sodium chloride the diazoamino compound is obtained in form of yellow, easily water soluble leaflets. In its free state the compound corresponds to the following formula:

Example 11.188 parts by weight of 4- nitro-l-naphthylamine are diazotized in the usual manner with 69 parts by weight of sodium nitrite, and the diazo solution is caused to react upon 331,5 parts by weight of the sodium salt of 4-chloroaniline-2.S-disulfonic acid in the presence of an acid-binding agent. When the coupling iscomplete, the sodium salt of the diazoamino compound formed, having in its free state the following formula: L

is salted out by the addition of sodium chloride.

Example 12.-214 parts by Weight of 4'- ni-trol-aminodiphenyl are diazotized in 21.

hydrochloric acid solution with 69 parts by SOaH is separated by the addition of common salt,

Example 13.-On replacing in Example 11 188 parts by weight of i nitro-l-naphthyL amine by 293 parts by weight of the sodium salt of 1-aminoanthrachinone-2-sulfonic acid and proceeding in the same manner as described in Example 11, thesodium salt of the diazoamino compound, having in its free state the following formula:

- 'SIO3HV O: O-soa1 soun 00 is obtained. I

Ewample 1.4.227- parts by weight of 4- nitro-3-amino-carbazole are diazotized in a hydrochloric acid solution with 69 parts by weight of sodium nitrite. The diazo solution is neutralized by the addition of sodium acetate, and 331,5 parts by weight of the sodium salt of 4-ehloroaniline-2.5-disulfonic acid are added-thereto. When the coupling is complete, from the diazo solution, rendered sodaalkaline, the sodium salt of the diazoamino compound, having in its free state the following formula: j

IIIO2 7 N=N-NHQ NH 50:11

is separated in the usual manner. 1;"!

no I

, tizable amine suitable for producing azodyei This in acontinuation-in-part of our application Ser. No. 377,075, filed July 9, 1929. I

VVeclaimz, I

1. As new products diazoam'ino compounds of the probable general formula:

i a wherein R stands for the radical of a diazostuffs which is at least once substituted by a substituent selectedfrom the group consisting of the sulfonic acid group, the carboxylic acid. group, a carboxylic acid ester group,

the arylsulfone group, the nitro group and halogen, and which may be further substi- E tnted alkyl oralkoxy, n stands forone of 7 of the probablegeneral formula:

i the numbers one to 'three,:a nd wherein the 2. As new products diazoamino compounds wherein 'Rstands for a benzene nucleus which isat least once substituted bya substituent selected from the group consisting of the sulfonic acid group, the carboxylic acid group, a carboxylic'acid ester group the arylsulfone group, the nitro'group and halogen, andwhich may be further substitutedby alkyl or alkoxy, 0?, stands" for one of the numbers one to three, and wherein the benzene nucleus R may be further substituted by substituents of the group consisting of alkyl,-"alkoxy and halogen, being in form of'their alkali metal "salts'generallyr greyis'h to orange crystalline powders, stable towards heat, percussion,

zene nucleus R maybe further substituted by substituents of" the' group consistingof alkyl, alkoxy and halogen, being in form of their alkali metal salts generally greyish to orange crystalline powders, stable towards; heat, percussion, friction and neutrally and alkaline reacting substances, and being split 7 up in aqueous solution into the two starting 7 components by the'a'ddition of acid, reacting agents. t a

4. As new products diazoamino'compounds of the probable general formula:

' soarr;

wherein :v'stands for a nitro group or halogen, and wherein the benzene nucleus It may be further substituted by halogen, a nitro group, alkyl or alkoxy, being in form of their alkali metal salts generally greyish to orange crysfltalline' powders, stable towardsheat, percussion, friction and neutrally and alkaline reacting substances, and being split up in aqueous solution into the two starting components by the addition of acid reacting agents. Y

'5. As a new'product the diazoamino 'compound of the followingformula:

" v v S|O=H 0zNON=nnnC O1 oon, sonar being in the form of its alkali metal salts a yellowish, crystalline powder, easily soluble in water, stable towards heat, percussion, friction and neutrally and alkaline reacting substances, and being split up in aqueous solution into the two starting components by the addition of acid reacting agents. d

In testimony whereof, we afiix our signatures. I

. WINFRIDHENTRIGH. 'ERNST TIETZE.

A'N TON OSSENBEGK: PETERBACKES.

friction and neutrally and alkaline reacting substances, and being split up in aqueous s0- -lut1on into the two startmg components by --the a'dditionof acid reacting agents. 1

. 3;. As new products diazoaminoco'mpounds of-the probablev general formula:

N=N-NH R (S0311),

wherein m stands for a nitro group or halogen, and wherein the benzene nucleus B may be further substituted by halogen, a nitro group, alkyl or alkoxy, 7?, stands for one of the numbers oneto three, and wherein the benlOO 

